JP2010209472A - Target for vaporizing under electron beam, method for manufacturing the same, thermal barrier material and coating obtained from the target, and mechanical parts including the coating - Google Patents
Target for vaporizing under electron beam, method for manufacturing the same, thermal barrier material and coating obtained from the target, and mechanical parts including the coating Download PDFInfo
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Abstract
Description
本発明は、電子ビームを受けて気化させる目的のセラミック粉末でできた棒の形態の複合ターゲットに関するものであり、前記の棒はジルコニアおよび少なくとも1種のジルコニア安定剤を含み、本発明はその製造方法にも関する。 The present invention relates to a composite target in the form of a rod made of ceramic powder for the purpose of receiving and vaporizing an electron beam, said rod comprising zirconia and at least one zirconia stabilizer, the present invention producing it Also related to the method.
本発明は、このようなターゲットに電子ビームを当て蒸着させることによって形成され、セラミックでできた、低い熱伝導率および高い熱機械強度を有する遮熱材の作成にも関する。 The present invention also relates to the production of a thermal barrier made of ceramic, having a low thermal conductivity and a high thermomechanical strength, formed by evaporating an electron beam on such a target.
本発明は、遮熱材などを含むセラミックコーティング、およびこれらのコーティングを含む超合金機械部品にも関する。 The present invention also relates to ceramic coatings including heat shields and the like, and superalloy machine parts including these coatings.
特に航空機の分野においては、ターボマシンの効率を高め、燃費ならびにガスおよび未燃焼燃料の環境汚染性排出物を減少させようとして、燃料の燃焼は化学量論に近い条件で行われている。こうした状況に伴って、燃焼室を出てタービンに向かうガスの温度が上昇している。 In particular, in the aircraft field, fuel combustion is carried out under near-stoichiometric conditions in an attempt to increase turbomachine efficiency and reduce fuel consumption and environmentally polluting emissions of gas and unburned fuel. With such a situation, the temperature of the gas leaving the combustion chamber and going to the turbine is rising.
したがって、タービンブレード(中空ブレード)を冷却する技術を改良することにより、および/または高温耐性に関するこの様な材料の特性を改善することにより、タービン中で使用する材料をこの温度上昇に適合させることが必要になった。この第2の技術は、ニッケルおよび/またはコバルトをベースとする超合金の使用とあいまって、遮熱材として知られる断熱性材料のコーティングを堆積することを含め、種々の解決策をもたらした。 Therefore, adapting the materials used in the turbine to this temperature increase by improving the technology of cooling turbine blades (hollow blades) and / or improving the properties of such materials with respect to high temperature resistance. Needed. This second technique, combined with the use of nickel and / or cobalt based superalloys, has provided various solutions, including depositing a coating of insulating material known as a thermal barrier.
定常的な運転条件では、冷却された部品に関して、セラミックコーティングは、厚さ約150マイクロメートル(μm)のコーティングに対して全体で200℃を超える差のある場合に、そのコーティングを通して温度勾配を確立することが可能である。例えばコーティングの基質を形成している下地金属の運転温度はその勾配によって低下し、したがって、必要とする冷却用空気の体積を著しく節約し、ならびに部品の寿命およびタービンエンジンの比燃費を顕著に改善する。 Under steady operating conditions, for a cooled part, the ceramic coating establishes a temperature gradient through the coating when there is a total difference of more than 200 ° C. for a coating of approximately 150 micrometers (μm) thickness. Is possible. For example, the operating temperature of the underlying metal forming the substrate of the coating is reduced by its gradient, thus significantly saving the volume of cooling air required and significantly improving component life and turbine engine specific fuel consumption. To do.
もちろん、遮熱材の特性ならびに特に基質との結合性を改善するために、基質とコーティングとの間に下地層を含めることが可能である。特に、場合によって白金、クロム、パラジウム、ルテニウム、イリジウム、オスミウム、ロジウム、またはこれら金属の混合物から選択された金属、および/またはジルコニウム(Zr)、ハフニウム(Hf)、およびイットリウム(Y)から選択された反応性元素を含むニッケルアルミニド、および/またはMCrAlY型の合金(Mはニッケル、コバルト、鉄、またはこれらの混合物から選択された金属)を含有する、1種または複数のアルミニドで構成された下地層を作成することが知られている。 Of course, it is possible to include an underlayer between the substrate and the coating in order to improve the properties of the heat shield as well as in particular its binding to the substrate. In particular, optionally selected from platinum, chromium, palladium, ruthenium, iridium, osmium, rhodium, or a mixture of these metals, and / or selected from zirconium (Zr), hafnium (Hf), and yttrium (Y). Composed of one or more aluminides containing nickel aluminides containing reactive elements and / or MCrAlY type alloys (where M is a metal selected from nickel, cobalt, iron or mixtures thereof) It is known to create an underlayer.
通常セラミックコーティングは、コーティングされる部品の上に、スプレー法(特にプラズマスプレー)、あるいは物理的蒸着技術、すなわち蒸着法、特に真空蒸着用容器内で電子の衝撃下に蒸着されるコーティングを形成する電子ビーム物理的蒸着法(EB−PVD)のいずれかによって蒸着される。 Usually ceramic coatings form a coating on the part to be coated by spraying (especially plasma spraying), or by physical vapor deposition techniques, i.e. vapor deposition, in particular in a vacuum deposition vessel, deposited under electron impact. Deposited by either electron beam physical vapor deposition (EB-PVD).
スプレーされたコーティングに関しては、ジルコニアをベースとした酸化物がプラズマスプレー型の技法によって堆積され、溶融されて次いで衝突で急冷された多量の液滴で構成されたコーティングの形成をもたらし、不完全に緻密化されて一般に50μm〜1ミリメートル(mm)の範囲にある厚みをもつ沈着物を形成するために平らにされ積み重ねられる。 For sprayed coatings, zirconia-based oxides are deposited by plasma spray-type techniques, resulting in the formation of coatings composed of large numbers of droplets that are melted and then quenched by impact, resulting in incomplete It is flattened and stacked to form a deposit that is densified and generally has a thickness in the range of 50 μm to 1 millimeter (mm).
物理的に堆積させられたコーティング、特に電子衝撃を受けた気化によって堆積させられたコーティングは、被覆される表面にほぼ垂直に配向した柱状物の集まりででき、20μm〜600μmの範囲にある厚みのコーティングになる。柱状物の間の空間は、コーティングが、稼動温度において超合金基質とは異なった伸びによる、およびブレードの回転による遠心機械応力による、熱機械応力を効果的に補償することを可能にして、有利である。こうして、高温での熱疲労を受けたときに長寿命を有する部品が得られる。 A physically deposited coating, in particular a coating deposited by electron impact vaporization, consists of a collection of pillars oriented substantially perpendicular to the surface to be coated, with a thickness in the range of 20 μm to 600 μm. Become a coating. The space between the columns allows the coating to effectively compensate for the thermomechanical stress due to elongation different from the superalloy substrate at operating temperature and due to centrifugal mechanical stress due to blade rotation. It is. Thus, a part having a long life when subjected to thermal fatigue at a high temperature is obtained.
通常あるように、このような遮熱材は、遮熱材を含む機械部品の外部コーティングと、部品を構成している材料を形成するコーティングの基質との間で、熱伝導性における不連続性をもたらす。 As is usual, such a heat shield is a discontinuity in thermal conductivity between the outer coating of the machine part containing the heat shield and the substrate of the coating that forms the material that makes up the part. Bring.
熱伝導性に大きな不連続性をもたらす遮熱材は、コーティングと基質の間、さらに正確には、下地層とセラミック遮熱材の界面において、分断する高いリスクを受けていることが認められるのが通例である。 It is recognized that heat shields that provide a large discontinuity in thermal conductivity are subject to a high risk of breakage between the coating and the substrate, and more precisely at the interface between the underlayer and the ceramic heat shield. Is customary.
現在、約1500℃の表面温度に、したがって基質内では約1300℃に上昇するのに、耐える機械部品を可能にする遮熱材組成物を得ることが望まれている。現在使用されている遮熱材は、約1200℃〜1300℃の表面温度に、したがって基質内が約1000℃〜1100℃に、耐える機械部品を可能にしている。 Currently, it is desirable to have a thermal barrier composition that allows a mechanical component to withstand a surface temperature of about 1500 ° C. and thus rise to about 1300 ° C. within the substrate. Currently used heat shields allow mechanical parts to withstand surface temperatures of about 1200 ° C. to 1300 ° C., and thus about 1000 ° C. to 1100 ° C. within the substrate.
膨張係数は基質を構成する超合金に近いものを有し、極めて低い熱伝導性の、ジルコニアによって構成されたベース材料から得られた遮熱材を使用することが知られている。 It is known to use a thermal barrier obtained from a base material composed of zirconia having an expansion coefficient close to that of the superalloy constituting the substrate and having a very low thermal conductivity.
本発明は、電子ビームを当ててターゲットを気化して得られる、コーティングの型に関する。使用したターゲットは電子ビームによって照射されたときに熱衝撃を受け、特にターゲットが欠陥および/または不規則性を示しているなら、その熱衝撃はターゲットの破壊をもたらしうる。ターゲットが破壊した場合、規則的に蒸発することによって材料を放出することがもはやできず、これ以上使用できない。 The present invention relates to a coating mold obtained by evaporating a target by applying an electron beam. The target used is subject to thermal shock when irradiated by the electron beam, and the thermal shock can lead to destruction of the target, especially if the target exhibits defects and / or irregularities. If the target breaks, the material can no longer be released by regular evaporation and can no longer be used.
欧州特許出願第1,055,743号は電子ビーム蒸発によって堆積できる材料に関するもので、この場合、照射によって温度が上昇したときに生じる材料の体積変化を、温度が500℃から1200℃に上昇するに従って正方晶ジルコニアに変化する単斜晶ジルコニアとの間での相転移によって引き起こされる4%の体積減少により、少なくとも部分的に補償することが望まれる。より正確には、この補償が極めて広い温度範囲で生じるのを確実にするために、単斜構造の粉末の粒子径を広い分布にする措置が講じられる。 European Patent Application No. 1,055,743 relates to materials that can be deposited by electron beam evaporation, in which case the volume change of the material that occurs when the temperature is increased by irradiation increases the temperature from 500 ° C. to 1200 ° C. It is desirable to at least partially compensate for the 4% volume reduction caused by the phase transition with monoclinic zirconia that changes to tetragonal zirconia according to More precisely, in order to ensure that this compensation occurs in a very wide temperature range, measures are taken to widen the particle size of the monoclinic powder.
欧州特許第1,055,743号は、熱衝撃に耐える性能を改善する目的で、単斜晶ジルコニアを25%〜90%の濃度で、好ましくは40%〜85%の範囲で、使用することも提供している。ドイツ特許第4,302,167号にあるように、熱衝撃に対する改良された耐性は、正方晶相と単斜晶相の間での相転移の最中のマイクロクラックの出現によってもたらされ、温度が降下する間、このマイクロクラックはクラックが成長するのを阻止するために、熱衝撃エネルギーを吸収することができ、したがって材料が破壊するのを防ぐ。欧州特許第1,055,743号によれば、単斜晶ジルコニアの上述した2つの役割が、熱衝撃に対する耐性を高めるのに役立つ。 EP 1,055,743 uses monoclinic zirconia at a concentration of 25% to 90%, preferably in the range of 40% to 85%, for the purpose of improving the performance to withstand thermal shock. Also offers. As in German Patent 4,302,167, improved resistance to thermal shock is brought about by the appearance of microcracks during the phase transition between the tetragonal and monoclinic phases, While the temperature drops, this microcrack can absorb thermal shock energy to prevent the crack from growing, thus preventing the material from breaking. According to EP 1,055,743, the above two roles of monoclinic zirconia help to increase the resistance to thermal shock.
欧州特許第1,055,743号によれば、ターゲットは、こうした数値範囲の外では使用できない。より正確には、ジルコニアの単斜晶相の含有率が25%未満である場合、相転移での体積減少による、蒸発の最中の熱膨張の補償が低下して、マイクロクラックの割合が少なくなりすぎ、したがって耐熱衝撃性を限定する。ジルコニアの単斜晶相含有率が90%を超える場合、蒸発に固有の温度上昇に続く冷却の最中には、正方晶ジルコニアから単斜晶ジルコニアに転移する相変化により誘導される体積膨張が大きすぎて、したがってクラック(シームまたは急冷クラック)を招き、ターゲットの強度を大きく低下させ、その破壊に至りうる。 According to EP 1,055,743, the target cannot be used outside these numerical ranges. More precisely, when the content of the monoclinic phase of zirconia is less than 25%, the compensation for thermal expansion during evaporation due to volume reduction at the phase transition is reduced, and the proportion of microcracks is small. Too much, thus limiting the thermal shock resistance. When the monoclinic phase content of zirconia exceeds 90%, during the cooling following the temperature rise inherent to evaporation, there is a volume expansion induced by the phase change from tetragonal zirconia to monoclinic zirconia. It is too large, thus causing cracks (seam or quenching cracks), greatly reducing the strength of the target and leading to its destruction.
本発明の目的は、棒の形態をした、ジルコニアと少なくとも1種のジルコニア安定剤を含むセラミック粉末の1種または複数の混合物で構成され、電子ビームを当てて蒸発するように設計された、複合ターゲットを得ることを可能にする解決策を提供することであり、それは再現可能な方法で容易に実施できて、良好な品質のターゲットを与える。 The object of the present invention is a composite composed of one or more mixtures of zirconia and ceramic powder containing at least one zirconia stabilizer in the form of a rod, designed to evaporate upon exposure to an electron beam. It is to provide a solution that makes it possible to obtain a target, which can be easily implemented in a reproducible way and gives a good quality target.
したがって本発明の目的は、ターゲットの組成と同一の組成を有する堆積セラミックス層を得るために、電子ビームを受けて気化させるためのセラミックターゲットが得られることを可能にすることである。 Accordingly, an object of the present invention is to make it possible to obtain a ceramic target for receiving and vaporizing an electron beam in order to obtain a deposited ceramic layer having the same composition as that of the target.
この目的のために、本発明は、電子ビームを受けて蒸発するためのセラミック粉末でできた棒の形態をした複合ターゲットを提供するもので、このターゲットはジルコニアと少なくとも1種のジルコニア安定剤とを含み、安定剤は2%〜30%の範囲にあるモル含有率で含まれ、ジルコニアは90%超の単斜晶相から形成される特徴がある。 To this end, the present invention provides a composite target in the form of a rod made of ceramic powder for receiving and evaporating an electron beam, the target comprising zirconia and at least one zirconia stabilizer. The stabilizer is included with a molar content ranging from 2% to 30%, and zirconia is characterized by being formed from a monoclinic phase of greater than 90%.
驚くべきことに、欧州特許第1,055,743号の教示に反して、単斜晶ジルコニアの90%を超える含有率は、求められているターゲットの冷却時の強度特性および熱衝撃への耐性と完全に両立する。 Surprisingly, contrary to the teachings of EP 1,055,743, the content of monoclinic zirconia in excess of 90% is the required strength properties of the target during cooling and resistance to thermal shock. And perfectly compatible.
本発明は、この用途で最適である機械特性をもつ、すなわち熱衝撃に対して良好な耐性を提供するためにかなり柔軟な、それでいて損傷を受けることなくターゲットを取り扱うことが可能な十分な強度のターゲットを得ることを可能にした。 The present invention has mechanical properties that are optimal for this application, i.e. it is fairly flexible to provide good resistance to thermal shock, yet strong enough to handle the target without damage. Made it possible to get a target.
90%を超える含有率でジルコニアの単斜晶相を示すターゲットの気化挙動は、ターゲットの別の特性、特に細孔径、比重、および気孔率の変動には、影響がより小さいことが分った。 It has been found that the vaporization behavior of a target exhibiting a monoclinic phase of zirconia with a content of more than 90% has a lesser effect on other properties of the target, in particular pore diameter, specific gravity and porosity variation. .
例えば、一定の比重で、0.4μm〜1.5μmの範囲での細孔径の変動、または一定の細孔径で、2.8〜3.3の範囲での比重の変動は、気化によって堆積させる最中での挙動に関して、またはこの堆積によって得られたコーティングの特性に関して、同じ結果になることが観察された。 For example, fluctuations in pore diameters in the range of 0.4 μm to 1.5 μm at a constant specific gravity or fluctuations in specific gravity in the range of 2.8 to 3.3 at a constant pore diameter are deposited by vaporization. It has been observed that the same results are obtained with respect to the behavior in the middle or with respect to the properties of the coating obtained by this deposition.
ターゲットの特性の上述した変動は、粉末のバッチを交換したとき、したがって粉末中の粒子の平均粒子径および比表面積が変化したときに起こりうる。粉末の一つのバッチから別のバッチに換えると、粒子径または比表面積の小さな変動がしばしば観察される。 The aforementioned variations in target properties can occur when changing a batch of powder, and thus when the average particle size and specific surface area of the particles in the powder change. When changing from one batch of powder to another, small variations in particle size or specific surface area are often observed.
したがって、ターゲット中で90%を超える含有率でジルコニアの単斜晶相を提供することを選択することにより、製造パラメータを修正することなく、あるいは使用する粉末の変動する特性値に拘わらず、同じターゲットの製造方法を使うことが可能である。 Therefore, by choosing to provide a monoclinic phase of zirconia in the target with a content of more than 90%, the same without modification of the production parameters or regardless of the varying characteristic values of the powder used It is possible to use target manufacturing methods.
ターゲットにおいては、前記ジルコニアは98%超の単斜晶相から形成されることが好ましい。 In the target, the zirconia is preferably formed from more than 98% monoclinic phase.
好ましい処理では、前記安定剤は、希土類酸化物、酸化タンタル、および酸化ニオブから形成される群に属する少なくとも1種の元素を含む。この点に関して、希土類の語句は、ランタニド(ランタン、セリウム、プラセオジミウム、ネオジウム、プロメチウム、サマリウム、ユーロピウム、ガドリニウム、テルビウム、ジスプロシウム、ホルミウム、エルビウム、ツリウム、イッテルビウム、およびルテチウム)、ならびにスカンジウムおよびイットリウムを示すのに使用される。 In a preferred treatment, the stabilizer comprises at least one element belonging to the group formed from rare earth oxides, tantalum oxide, and niobium oxide. In this regard, the term rare earth refers to lanthanides (lanthanum, cerium, praseodymium, neodymium, promethium, samarium, europium, gadolinium, terbium, dysprosium, holmium, erbium, thulium, ytterbium, and lutetium), and scandium and yttrium. Used for.
ターゲットの比重は、3.9未満が好ましく、2.5〜3.3の範囲にあるのが好ましい。 The specific gravity of the target is preferably less than 3.9, and preferably in the range of 2.5 to 3.3.
また、ターゲットは、2μm未満の平均細孔径d50(0.2μm〜1.5μmの範囲にあるのが好ましく、0.4μm〜1.2μmの範囲にあるのがより好ましい)、30%〜50%の気孔率を示すのが好ましい。 Further, the target has an average pore diameter d 50 of less than 2 μm (preferably in the range of 0.2 μm to 1.5 μm, more preferably in the range of 0.4 μm to 1.2 μm), 30% to 50 % Porosity is preferred.
平均細孔径によって、およびターゲットの比重によって構成されるこれら2つのパラメータは、ターゲットの機械強度に、および気化の最中での挙動に、および特に熱衝撃に対する耐性に影響を及ぼす。これらの因子は、適切に出発原料を選択することにより、および製造パラメータを選択することにより、制御することができる。 These two parameters, constituted by the average pore size and by the specific gravity of the target, influence the mechanical strength of the target, and the behavior during vaporization, and in particular the resistance to thermal shock. These factors can be controlled by appropriately selecting starting materials and by selecting manufacturing parameters.
本発明は、高さに沿って変化する組成を示すターゲットにも関する。 The invention also relates to a target that exhibits a composition that varies along the height.
本発明は、先に定義したような、棒の形態をした、セラミック粉末からなり、電子ビームを受けて気化する目的のための、複合ターゲットの製造方法をも提供する。本発明によれば、この方法は、
a)バインダーとジルコニアおよび少なくとも1種のジルコニア安定剤を含む粉末とからなり、前記ジルコニアの90%超が単斜晶相から形成される第1組成物を含む、少なくとも第1混合物を調製するステップと、
b)前記混合物を型に導入するステップと、
c)前記の型内で混合物を圧縮成形するステップと、
d)圧縮成形した混合物を1500℃未満の温度で焼成するステップを、
含むことに特徴がある。
The invention also provides a method for producing a composite target, as defined above, made of a ceramic powder in the form of a rod, for the purpose of receiving and vaporizing an electron beam. According to the invention, this method comprises:
a) preparing at least a first mixture comprising a first composition comprising a binder and a powder comprising zirconia and at least one zirconia stabilizer, wherein more than 90% of said zirconia is formed from a monoclinic phase. When,
b) introducing the mixture into a mold;
c) compression molding the mixture in the mold;
d) firing the compression molded mixture at a temperature of less than 1500 ° C.
It is characterized by including.
安定化温度は、考察中の粉末系の関数である。それは通常1500℃未満であり、900℃〜1100℃の範囲にあるのが好ましい。 The stabilization temperature is a function of the powder system under consideration. It is usually below 1500 ° C and is preferably in the range of 900 ° C to 1100 ° C.
ターゲット中での90%超の単斜晶相含有率を保持するためには、焼成温度は十分に低くなければならず、すなわち粉末の粒子間に確立されたブリッジに伴うジルコニアの安定化を制限すると、熱衝撃に対する耐性の低下を招く。 In order to maintain a monoclinic phase content of more than 90% in the target, the calcination temperature must be low enough, ie limiting the stabilization of zirconia with the bridges established between the powder particles. As a result, the resistance to thermal shock is reduced.
純粋なジルコニア粉末、すなわち安定化されていない粉末を使用すると、ステップa)の中で、多様な組成をもつターゲットを低コストで作成することが可能になる。市場では、一定の含有率のY2O3、MgO、CaO、およびCeO2で構成されたより一般的な安定剤(特に、ZrO2の量に対して、Y2O3が3%、4%、または5%)で安定化された、ジルコニア類が一般に販売されている。別の型の安定化剤(例えば、希土類酸化物)により、または特殊な含有率で安定化された粉末を合成するのは高価になる。合成は、化学的方法(高価な前駆体)、または物理的方法(混合物の焼成、次いで粉砕および所望の粒径範囲を得るための篩い分け)で行われる。さらに、原料粉末の1種または複数の混合物を使用することで、ターゲットの長さに沿った全ての断面で化学組成を制御することができ、したがって、必要に応じて、コーティングの厚みの中で所与の化合物の含有率を変えることが可能である。したがってこの方法は、異なる組成をもつ複数のセグメントから作成される複合ターゲットを作成する場合、前もって数多くの安定化ジルコニア混合物の合成をしなくて済む。 The use of pure zirconia powder, i.e. unstabilized powder, makes it possible to produce targets with various compositions at low cost in step a). On the market, more common stabilizers composed of a constant content of Y 2 O 3 , MgO, CaO and CeO 2 (particularly 3%, 4% Y 2 O 3 relative to the amount of ZrO 2 ). , Or 5%), are generally sold. It is expensive to synthesize powders stabilized with another type of stabilizer (eg rare earth oxides) or with a special content. The synthesis is carried out by chemical methods (expensive precursors) or physical methods (calcination of the mixture followed by grinding and sieving to obtain the desired particle size range). In addition, by using one or more mixtures of raw powders, the chemical composition can be controlled at all cross-sections along the length of the target, and therefore, if necessary, within the coating thickness It is possible to vary the content of a given compound. Thus, this method eliminates the need to synthesize a number of stabilized zirconia mixtures in advance when creating composite targets made from multiple segments having different compositions.
バインダーは水性、すなわち水分を含むものが好ましいが、ポリビニルアルコールなどの有機バインダーを含めてもよい。 The binder is preferably aqueous, that is, containing water, but may contain an organic binder such as polyvinyl alcohol.
好ましい処理では、前記安定剤は、希土類酸化物、酸化タンタル、および酸化ニオブから作成される群に属す少なくとも1種の元素を含む。この点に関して、希土類の語句は、ランタニド(ランタン、セリウム、プラセオジミウム、ネオジウム、プロメチウム、サマリウム、ユーロピウム、ガドリニウム、テルビウム、ジスプロシウム、ホルミウム、エルビウム、ツリウム、イッテルビウム、およびルテチウム)、ならびにスカンジウムおよびイットリウムを示すのに使用される。 In a preferred treatment, the stabilizer comprises at least one element belonging to the group made from rare earth oxides, tantalum oxide, and niobium oxide. In this regard, the term rare earth refers to lanthanides (lanthanum, cerium, praseodymium, neodymium, promethium, samarium, europium, gadolinium, terbium, dysprosium, holmium, erbium, thulium, ytterbium, and lutetium), and scandium and yttrium. Used for.
ステップa)が、バインダーとジルコニアおよび少なくとも1種のジルコニア安定剤を含む粉末とから作成される第2組成物を有する、少なくとも第2の混合物を調製することを含み、前記ジルコニアが90%超が単斜晶相からなり、ステップb)は第1の混合物と第2の混合物を続けて導入し、それによって高さに沿って変化する組成を有するターゲットを得ることが好ましい。 Step a) comprises preparing at least a second mixture having a second composition made from a binder and a powder comprising zirconia and at least one zirconia stabilizer, wherein the zirconia is greater than 90% Preferably, step b) consists of a monoclinic phase and subsequently introduces a first mixture and a second mixture, thereby obtaining a target having a composition that varies along the height.
前記セラミック粉末は、5μm〜30μmの範囲にある平均粒子径、あるいはグラム当り10平方メートル(m2/g)未満の比表面積、および3m2/g〜8m2/gの範囲にある比表面積を示すことが好ましい。 The ceramic powder exhibits an average particle diameter or specific surface area in grams per 10 square meters (m 2 / g) less than the specific surface area, and in the range of 3m 2 / g~8m 2 / g, in the range of 5μm~30μm It is preferable.
別の処理では、前記セラミック粉末は5μm未満の平均粒子径を示し、ステップa)は粉末をバインダー中に導入する前に粉末を焼成するサブステップを含む。 In another process, the ceramic powder exhibits an average particle size of less than 5 μm, and step a) includes a sub-step of firing the powder before introducing the powder into the binder.
この焼成ステップは、粉末の粒子径を、5μm〜30μmの範囲にある数値に再調整することを可能にする。 This firing step allows the powder particle size to be readjusted to a numerical value in the range of 5 μm to 30 μm.
本発明はまた、低い熱伝導率および高い熱機械強度をもつセラミック遮熱材を提供するもので、上記で指定された型のターゲットを、電子ビームを受けて気化させることにより形成され、超合金基質上に堆積することに特徴がある。 The present invention also provides a ceramic heat shield with low thermal conductivity and high thermomechanical strength, formed by evaporating a target of the type specified above upon receiving an electron beam, and a superalloy. It is characterized by depositing on the substrate.
本発明はまた、結合下地層、4%〜12%の範囲にある酸化イットリウムのモル含有率を有するイットリウム化ジルコニアをベースとする第1セラミック層、および前段落で定義された遮熱材で形成された第2セラミック層を含み、前記第1セラミック層が前記結合下地層と前記第2セラミック層の間に位置しているセラミックコーティングを提供する。 The invention also forms a bonded underlayer, a first ceramic layer based on yttrium zirconia having a molar content of yttrium oxide in the range of 4% to 12%, and a heat shield as defined in the previous paragraph. Providing a ceramic coating, wherein the first ceramic layer is located between the bonded underlayer and the second ceramic layer.
最後に、本発明は、超合金ででき、上記で指定された型のターゲットから得られた遮熱材を有するセラミックコーティングを含むことに特徴のある機械部品をも提供する。 Finally, the present invention also provides a mechanical component characterized in that it comprises a ceramic coating that is made of a superalloy and has a thermal barrier obtained from a target of the type specified above.
特に、機械部品に関する以下の有利な構成は、本発明に従って実施できる。
・前記セラミックコーティングをその上に堆積させる、結合下地層をさらに含み、
・前記結合下地層は酸化により保護アルミナ層を形成するのに適した合金によって構成され、
・前記結合下地層はMCrAlY型の合金で構成され、Mはニッケル、コバルト、鉄、およびこれら金属の混合物から選択された金属であり、
・前記結合下地層が、場合によって白金、クロム、パラジウム、ルテニウム、イリジウム、オスミウム、ロジウム、またはこれら金属の混合物から選択された金属、および/またはジルコニウム(Zr)、ハフニウム(Hf)、およびイットリウム(Y)から選択された反応性元素を含むニッケルアルミニドで構成され、および/または
・前記セラミックコーティングがさらに、前記下地層の上に、4%〜12%の範囲にある酸化イットリウムのモル含有率を有するイットリウム化ジルコニアをベースとしたセラミック層を含む。
In particular, the following advantageous configurations for machine parts can be implemented according to the invention.
-Further comprising a bond underlayer on which the ceramic coating is deposited;
The bond underlayer is composed of an alloy suitable for forming a protective alumina layer by oxidation;
The bond underlayer is composed of an MCrAlY type alloy, and M is a metal selected from nickel, cobalt, iron, and mixtures of these metals;
The bond underlayer is optionally a metal selected from platinum, chromium, palladium, ruthenium, iridium, osmium, rhodium, or a mixture of these metals, and / or zirconium (Zr), hafnium (Hf), and yttrium ( Y) composed of nickel aluminide containing a reactive element selected from: and / or the ceramic coating further has a molar content of yttrium oxide in the range of 4% to 12% on the underlayer A ceramic layer based on yttrium zirconia having the following:
本発明のこの他の有利な点および特徴的な点は、限界を設けずに与えられるターゲットの実施形態の以下の記述を読むと、明らかになる。 Other advantages and features of the present invention will become apparent upon reading the following description of target embodiments given without limitation.
以下の条件下にターゲットを調製した。
・>99.9%の純度を有する、ZrO2(100%単斜晶、平均粒子径d50=25μm、および比表面積1.20m2/g)およびY2O3粉末(ZrO2の量に対して4モル%、平均粒子径d50=5.16μm)を混合し、
・全混合物に対して3.5重量%の含有率で、ポリビニルアルコールの形のバインダーを添加し、
・この混合物を型に導入し、
・100バールの圧を加え(等方圧加圧)、および
・1300℃で1時間焼成した。
A target was prepared under the following conditions.
ZrO 2 (100% monoclinic crystal, average particle size d 50 = 25 μm, specific surface area 1.20 m 2 / g) and Y 2 O 3 powder (in the amount of ZrO 2 ) with a purity of> 99.9% 4 mol%, average particle diameter d 50 = 5.16 μm)
-Add a binder in the form of polyvinyl alcohol at a content of 3.5% by weight with respect to the total mixture;
・ Introduce this mixture into the mold,
• Pressure of 100 bar was applied (isostatic pressing) and • baked at 1300 ° C for 1 hour.
その様にして得られたターゲットは、比重3.27、平均細孔径d50=2.04μm、気孔率44%、単斜結晶相含有率91.7%、熱膨張係数6.8×10−2、および全体積収縮率3.7%を示した。 The target thus obtained has a specific gravity of 3.27, an average pore diameter d 50 = 2.04 μm, a porosity of 44%, a monoclinic crystal phase content of 91.7%, and a thermal expansion coefficient of 6.8 × 10 − 2 and a total volume shrinkage of 3.7%.
それでも、ターゲットに成形した棒は850℃までの予熱でクラックが生じ、堆積させることは全くできなかった。 Nevertheless, the rod formed on the target was cracked by preheating up to 850 ° C. and could not be deposited at all.
以下の条件下にターゲットを調製した。
・>99.9%の純度を有する、ZrO2(100%単斜晶、平均粒子径d50=16.7μm、および比表面積4.4m2/g)およびY2O3粉末(ZrO2の量に対して4モル%、平均粒子径d50=0.99μm)を混合し、
・全混合物に対して3.0重量%の含有率で、ポリビニルアルコールの形のバインダーを添加し、
・この混合物を型に導入し、
・1600バールの圧を加え(等方圧加圧)、および
・1000℃で1時間焼成した。
A target was prepared under the following conditions.
ZrO 2 (100% monoclinic crystal, average particle size d 50 = 16.7 μm, specific surface area 4.4 m 2 / g) and Y 2 O 3 powder (of ZrO 2 ) with a purity of> 99.9% 4 mol% with respect to the amount, average particle diameter d 50 = 0.99 μm),
Add a binder in the form of polyvinyl alcohol, with a content of 3.0% by weight relative to the total mixture,
・ Introduce this mixture into the mold,
• 1600 bar pressure applied (isostatic pressing) and • 1 hour baking at 1000 ° C.
その様にして得られたターゲットは、比重3.11、平均細孔径d50=0.75μm、気孔率44%、単斜結晶相含有率100%、熱膨張係数0.78×10−2、および全体積収縮率7.4%を示した。 The target thus obtained has a specific gravity of 3.11, an average pore diameter d 50 = 0.75 μm, a porosity of 44%, a monoclinic crystal phase content of 100%, a thermal expansion coefficient of 0.78 × 10 −2 , And the total volume shrinkage was 7.4%.
この棒で首尾よく堆積物を作ることができ、遮熱材を形成するセラミック層を創作した。 This rod was able to create a deposit successfully and created a ceramic layer that forms a heat shield.
以下の条件下にターゲットを調製した。
・>99.9%の純度を有する、ZrO2(100%単斜晶、平均粒子径d50=21.8μm、および比表面積7.7m2/g)およびDy2O3粉末(ZrO2の量に対して12モル%、平均粒子径d50=2.97μm)を混合し、
・全混合物に対して4.0重量%の含有率で、ポリビニルアルコールの形のバインダーを添加し、
・この混合物を型に導入し、
・1600バールの圧を加え(等方圧加圧)、および
・1000℃で1時間焼成した。
A target was prepared under the following conditions.
ZrO 2 (100% monoclinic, average particle size d 50 = 21.8 μm, and specific surface area 7.7 m 2 / g) and Dy 2 O 3 powder (of ZrO 2 ) with a purity of> 99.9% 12 mol% based on the amount, average particle diameter d 50 = 2.97 μm),
Add a binder in the form of polyvinyl alcohol at a content of 4.0% by weight with respect to the total mixture,
・ Introduce this mixture into the mold,
• 1600 bar pressure applied (isostatic pressing) and • 1 hour baking at 1000 ° C.
その様にして得られたターゲットは、比重3.14、平均細孔径d50=0.40μm、気孔率49%、単斜結晶相含有率95%、熱膨張係数0.55×10−2、および全体積収縮率9.5%を示した。 The target thus obtained has a specific gravity of 3.14, an average pore diameter d 50 = 0.40 μm, a porosity of 49%, a monoclinic crystal phase content of 95%, a thermal expansion coefficient of 0.55 × 10 −2 , And the total volume shrinkage was 9.5%.
この棒で首尾よく堆積物を作ることができ、遮熱材を形成するセラミック層を作成した。 This rod was able to successfully produce deposits and created a ceramic layer that formed a heat shield.
Claims (11)
b)前記混合物を型に導入するステップと、
c)前記型内で混合物を圧縮成形するステップと、
d)圧縮成形した混合物を1500℃未満の温度で焼成するステップと、
を含むことを特徴とする、ターゲットがセラミック粉末で作成され、電子ビームを受けて気化するように意図された、請求項1から6のいずれか一項に記載の棒の形態の複合ターゲットの製造方法。 a) preparing at least a first mixture comprising a first composition comprising a binder and a powder comprising zirconia and at least one zirconia stabilizer, wherein more than 90% of said zirconia is formed from a monoclinic phase. When,
b) introducing the mixture into a mold;
c) compression molding the mixture in the mold;
d) firing the compression molded mixture at a temperature below 1500 ° C .;
The production of a composite target in the form of a bar according to any one of claims 1 to 6, characterized in that the target is made of ceramic powder and is intended to evaporate upon receiving an electron beam Method.
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JP4571472B2 (en) | 2010-10-27 |
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US7429350B2 (en) | 2008-09-30 |
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